From Chalcogen Bonding to S-π Interactions in Hybrid Perovskite Photovoltaics.

The stability of hybrid organic-inorganic halide perovskite semiconductors remains a significant obstacle to their application in photovoltaics. To this end, the use of low-dimensional (LD) perovskites, which incorporate hydrophobic organic moieties, provides an effective strategy to improve their stability, yet often at the expense of their performance. To address this limitation, supramolecular engineering of noncovalent interactions between organic and inorganic components has shown potential by relying on hydrogen bonding and conventional van der Waals interactions. Here, the capacity to access novel LD perovskite structures that uniquely assemble through unorthodox S-mediated interactions is explored by incorporating benzothiadiazole-based moieties. The formation of S-mediated LD structures is demonstrated, including one-dimensional (1D) and layered two-dimensional (2D) perovskite phases assembled via chalcogen bonding and S-π interactions, through a combination of techniques, such as single crystal and thin film X-ray diffraction, as well as solid-state NMR spectroscopy, complemented by molecular dynamics simulations, density functional theory calculations, and optoelectronic characterization, revealing superior conductivities of S-mediated LD perovskites. The resulting materials are applied in n-i-p and p-i-n perovskite solar cells, demonstrating enhancements in performance and operational stability that reveal a versatile supramolecular strategy in photovoltaics.

Hierarchical Self-Assembly of Curved Aromatics: From Donor-Acceptor Porphyrins to Triply Periodic Minimal Surfaces.

A saddle-shaped π-extended zinc porphyrin containing a peripheral pyridyl ligand undergoes quantitative self-assembly into a cyclic trimer. The trimer has a prismatic structure with negatively curved side walls, which promote the formation of supramolecular organic frameworks stabilized by dispersion interactions. The first framework type, UWr-1, has the npo topology, with a hexagonal structure analogous to the Schwartz H triply periodic minimal surface. Co-crystallization of the trimer with either C60 and C70 produces the isomorphous cubic UWr-2 and UWr-3 phases, characterized by the ctn network topology and a structural relationship to the Fischer-Koch minimal surface S. All three phases contain complex labyrinths of solvent-filled channels, corresponding to very large probe-accessible volumes (68 % to 76 %). The UWr-2 network could be partly desolvated while retaining its long range dimensional order, indicating remarkable strength of the dispersion interactions in the crystal. A theoretical analysis of noncovalent interactions shows the role of geometrical matching between the negatively curved porphyrin units and positively curved fullerenes.

MOF/polymer hybrids through in situ free radical polymerization in metal-organic frameworks.

We use the free radical polymerization initiator 4,4'-azobis(cyanovaleric acid) coordinated to the open metal sites of metal-organic frameworks (MOFs) to give rise to highly uniform MOF/polymer hybrids. We demonstrate this strategy on two robust zirconium MOFs (NU-1000 and MOF-808), which are the most effective catalysts for degradation of chemical warfare nerve agents. The resulting hybrid materials maintain their hydrolytic catalytic activity and have substantially improved adhesion to polypropylene and activated carbon textile fibers, yielding highly robust MOF/polymer/textile hybrid systems. These composites are suitable for the green production of active protective clothing and filters capable of detoxifying organophosphorus warfare agents.

Zirconium-Based Metal-Organic Frameworks as Acriflavine Cargos in the Battle against Coronaviruses─A Theoretical and Experimental Approach.

In this study, we present a complementary approach for obtaining an effective drug, based on acriflavine (ACF) and zirconium-based metal-organic frameworks (MOFs), against SARS-CoV-2. The experimental results showed that acriflavine inhibits the interaction between viral receptor-binding domain (RBD) of spike protein and angiotensin converting enzyme-2 (ACE2) host receptor driving viral cell entry. The prepared ACF@MOF composites exhibited low (MOF-808 and UiO-66) and high (UiO-67 and NU-1000) ACF loadings. The drug release profiles from prepared composites showed different release kinetics depending on the local pore environment. The long-term ACF release with the effective antiviral ACF concentration was observed for all studied ACF@MOF composites. The density functional theory (DFT) calculations allowed us to determine that π-π stacking together with electrostatic interaction plays an important role in acriflavine adsorption and release from ACF@MOF composites. The molecular docking results have shown that acriflavine interacts with several possible binding sites within the RBD and binding site at the RBD/ACE2 interface. The cytotoxicity and ecotoxicity results have confirmed that the prepared ACF@MOF composites may be considered potentially safe for living organisms. The complementary experimental and theoretical results presented in this study have confirmed that the ACF@MOF composites may be considered a potential candidate for the COVID-19 treatment, which makes them good candidates for clinical trials.

Multi-Length Scale Structure of 2D/3D Dion-Jacobson Hybrid Perovskites Based on an Aromatic Diammonium Spacer.

Dion-Jacobson (DJ) iodoplumbates based on 1,4-phenylenedimethanammonium (PDMA) have recently emerged as promising light absorbers for perovskite solar cells. While PDMA is one of the simplest aromatic spacers potentially capable of forming a DJ structure based on (PDMA)An-1 Pbn I3n+1 composition, the crystallographic proof has not been reported so far. Single crystal structure of a DJ phase based on PDMA is presented and high-field solid-state NMR spectroscopy is used to characterize the structure of PDMA-based iodoplumbates prepared as thin films and bulk microcrystalline powders. It is shown that their atomic-level structure does not depend on the method of synthesis and that it is ordered and similar for all iodoplumbate homologues. Moreover, the presence of lower (n) homologues in thin films is identified through UV-Vis spectroscopy, photoluminescence spectroscopy, and X-ray diffraction measurements, complemented by cathodoluminescence mapping. A closer look using cathodoluminescence shows that the micron-scale microstructure corresponds to a mixture of different layered homologues that are well distributed throughout the film and the presence of layer edge states which dominate the emission. This work therefore determines the formation of DJ phases based on PDMA as the spacer cation and reveals their properties on a multi-length scale, which is relevant for their application in optoelectronics.

Immobilization of Rh(I) precursor in a porphyrin metal-organic framework - turning on the catalytic activity.

Two model porphyrin metal-organic frameworks were used for the incorporation of Rh(i) species by a post-synthetic metallation under mild conditions. As a result, new rhodium MOFs (Rh/MOFs), Rh/PCN-222 and Rh/NU-1102, were synthesized and structurally characterized. To illustrate the potential of this catalytic platform, we use Rh/MOFs as phosphine-free heterogeneous catalysts in the hydrogenation of unsaturated hydrocarbons under mild reaction conditions (30 °C and 1 atm H2). We found that for our Rh/MOFs an activation step is required during the first run of the catalytic process. The presence of Rh-CO moieties allowed us to monitor the activation pathway of the catalyst under a H2 atmosphere, by in situ Diffuse Reflectance Infrared Fourier Transform Spectroscopy (DRIFTS). After activation, the catalyst remains highly active during the subsequent catalytic cycles. This simple post-synthetic modification approach presents new possibilities for the utilization of Rh-based catalytic systems with robust porphyrin-based MOFs as supports.

Quest for an Efficient 2-in-1 MOF-Based Catalytic System for Cycloaddition of CO2 to Epoxides under Mild Conditions.

We have devised a straightforward tandem postsynthetic modification strategy for Zr-based metal-organic framework (MOF) materials, which resulted in a series of well-defined 2-in-1 heterogeneous catalysts, cat1-cat8, exhibiting high catalytic activity in the synthesis of cyclic carbonates under solvent-free and co-catalyst-free conditions. The materials feature precisely located co-catalyst moieties decorating the metal nodes throughout the bulk of the MOF and yield cyclic carbonates with up to 99% efficiency at room temperature. We use diffuse reflectance infrared Fourier transform (DRIFT) and solid-state nuclear magnetic resonance (NMR) measurements to elucidate the role of each component in this model catalytic reaction. Establishing a method to precisely control the co-catalyst loading allowed us to observe the cooperativity between Lewis acid sites and the co-catalyst in the 2-in-1 heterogeneous system.

Feeding a Molecular Squid: A Pliable Nanocarbon Receptor for Electron-Poor Aromatics.

A hybrid nanocarbon receptor consisting of a calix[4]arene and a bent oligophenylene loop ("molecular squid"), was obtained in an efficient, scalable synthesis. The system contains an electron-rich cavity with an adaptable shape, which can serve as a host for electron deficient guests, such as diquat, 10-methylacridinium, and anthraquinone. The new receptor forms inclusion complexes in the solid state and in solution, showing a dependence of the observed binding strength on the shape of the guest species and its charge. The interaction with the methylacridinium cation in solution was interpreted in terms of a 2:1 binding model, with K11 = 5.92(7) × 103 M-1. The solid receptor is porous to gases and vapors, yielding an uptake of ca. 4 mmol/g for methanol at 293 K. In solution, the receptor shows cyan fluorescence (λmaxem = 485 nm, ΦF = 33%), which is partly quenched upon binding of guests. Methylacridinium and anthraquinone adducts show red-shifted emission in the solid state, attributable to the charge-transfer character of these inclusion complexes.

Rational Design of Noncovalent Diamondoid Microporous Materials for Low-Energy Separation of C6-Hydrocarbons.

Selective separation of gases/vapors with similar physicochemical properties involves energetically costly distillation processes. Alternative separation processes based on shape-selective molecular sieving, taking place on porous frameworks (or membranes), are less energy demanding but require an optimal balance between selectivity and diffusion kinetics (permeability). Herein, we report a rational strategy to select an optimal soft noncovalent microporous material (NPM) suitable for the low-energy separation of C6-hydrocarbons with kinetic diameters in the range of 4.3-6.3 Å. This strategy is based on a Cambridge Structural Database search of diamondoid NPMs with a low packing factor, leading to the selection of an oxidotetrazinc cluster based diamondoid NPM network named DiaMM-1 containing tetrahedral voids of 336 Å3 (tetrahedron insphere diameter of 5.8 Å accessible through 8.2 Å triangular windows) suitable for this separation. Based on this result the fluorinated analogue DiaMM-2 was designed and synthesized. DiaMM-1 and DiaMM-2 exhibit permanent porosity and high thermal stability. The optimal combination of molecular crystal softness, pore size, and decoration of pore surface of DiaMM-1,-2 leads to high adsorbate diffusivity and low adsorption energy, allowing fast separation of hexane isomers and benzene/cyclohexane mixtures at low temperature.

Porous Silsesquioxane-Imine Frameworks as Highly Efficient Adsorbents for Cooperative Iodine Capture.

The efficient capture and storage of radioactive iodine (129I or 131I), which can be formed during nuclear energy generation or nuclear waste storage, is of paramount importance. Herein, we present highly efficient aerogels for reversible iodine capture, namely, porous silsesquioxane-imine frameworks (PSIFs), constructed by condensation of octa(3-aminopropyl)silsesquioxane cage compound and selected multitopic aldehydes. The resulting PSIFs are permanently porous (Brunauer-Emmet-Teller surface areas up to 574 m2/g), thermally stable, and present a combination of micro-, meso-, and macropores in their structures. The presence of a large number of imine functional groups in combination with silsesquioxane cores results in extremely high I2 affinity with uptake capacities up to 485 wt %, which is the highest reported to date. Porous properties can be controlled by the strut length and rigidity of linkers. In addition, PSIF-1a could be recycled at least four times while maintaining 94% I2 uptake capacity. Kinetic studies of I2 desorption show two strong binding sites with apparent activation energies of 77.0 and 89.0 kJ/mol. These energies are considerably higher than the enthalpy of sublimation of bulk I2.

Hybrid Triazine-Boron Two-Dimensional Covalent Organic Frameworks: Synthesis, Characterization, and DFT Approach to Layer Interaction Energies.

The conversion of 2,4,6-tris(4'-bromophenyl)-1,3,5-triazine to the respective triboronic acid was successfully accomplished by a simple triple Br/Li exchange followed by boronation. Further dehydrative condensation reactions with 2,3,6,7,10,11-hexahydroxytriphenylene or 2,3,6,7-tetrahydroxy-9,10-dilalkylanthracenes (R = Me, Et) resulted in materials featuring good porosity and sorption properties with the nitrogen uptake exceeding 500 cm3/g (STP) and SBET up to 1267 m2/g (T = 77.2 K). In addition, simple dehydration of this compound was employed for the preparation of a hybrid 2D COF composed of triazine, boroxine, and benzene rings. The formation of materials was confirmed by the IR analysis and NMR studies on water-decomposed samples. All obtained COFs exhibit high thermal stability with decomposition temperatures in the range of 400-600 °C. They also show quite different morphology ranging from regular 0.5-4 µm spherical and ellipsoidal clusters to 5-12 µm bent rodlike particles. The PXRD studies supported by periodic DFT modeling in Crystal09 package revealed the formation of crystalline 2D honeycomb-type lattices with eclipsed stacking models. In addition, the differences between boroxine-triazine material and related COF-1 and CTF-1 structures were investigated by comparing layer interaction energies, work function values as well as atomic charges and electrostatic potential maps plotted on the electron density surfaces. It demonstrates that the interactions between layers are enhanced by the stacking of triazine and boroxine rings. Finally, we have investigated the upper limit to space accessible volume using a procrystal electron density approach.

Structure investigations of group 13 organometallic carboxylates.

The octet-compliant group 13 organometallics with highly polarized bonds in the metal coordination sphere exhibit a significant tendency to maximize their coordination number through the formation of adducts with a wide range of neutral donor ligands or by self-association to give aggregates containing tetrahedral and higher coordinated aluminium centres, and even in some cases molecular complexes equilibrate with ionic species of different coordination numbers of the metal centre. This work provides a comprehensive overview of the structural chemistry landscape of the group 13 carboxylates. Aside from a more systematic approach to the general structural chemistry of the title compounds, the structure investigations of [R2M(µ-O2CPh)]2-type benzoate complexes (where M = B, Al and Ga) and their Lewis acid-base adducts [(R2M)(µ-O2CPh)(py-Me)] are reported. DFT calculations were also performed to obtain a more in-depth understanding of both the changes in the bonding of group 13 organometallic carboxylate adducts with a pyridine ligand.

Metal-Organic Framework Thin Films as Platforms for Atomic Layer Deposition of Cobalt Ions To Enable Electrocatalytic Water Oxidation.

Thin films of the metal-organic framework (MOF) NU-1000 were grown on conducting glass substrates. The films uniformly cover the conducting glass substrates and are composed of free-standing sub-micrometer rods. Subsequently, atomic layer deposition (ALD) was utilized to deposit Co(2+) ions throughout the entire MOF film via self-limiting surface-mediated reaction chemistry. The Co ions bind at aqua and hydroxo sites lining the channels of NU-1000, resulting in three-dimensional arrays of separated Co ions in the MOF thin film. The Co-modified MOF thin films demonstrate promising electrocatalytic activity for water oxidation.

Ultraporous, Water Stable, and Breathing Zirconium-Based Metal-Organic Frameworks with ftw Topology.

"Breathing" metal-organic frameworks (MOFs) are an emerging class of soft porous crystals (SPCs) with potential for high working capacity for gas storage applications. However, most breathing MOFs have low stability and/or low surface area. Here we report a water-stable, high surface area, breathing MOF of ftw topology, NU-1105. While Zr6-oxo clusters as nodes introduce water stability in NU-1105, its high surface area and breathing character stem from its pyrene-based tetracarboxylate (Py-FP) linkers, in which the fluorene units (F) in the FP "arms" play a key role in promoting breathing behavior. During gas sorption studies, the "closed pore" (cp) ↔ "open pore" (op) transition of NU-1105 occurs at a propane pressure of ∼3 bar. At 1 bar, NU-1105 is in its cp form and adsorbs less propane than it would in its op form, highlighting improved working capacity. In situ powder X-ray diffraction during propane sorption was used to track the cp ↔ op transition, and molecular modeling was used to elucidate the structure of the op and cp forms of NU-1105. According to TD-DFT calculations, the proposed conformations of the Py-FP linkers in the op and cp forms are consistent with the measured excitation and emission spectra of the op and cp forms of NU-1105. Similar structural transitions are also observed in the porphyrinic MOF NU-1104 depending on the identity of the porphyrin core; we observed breathing behavior if the constituent Por-PTP linker is nonmetalated.

A porous proton-relaying metal-organic framework material that accelerates electrochemical hydrogen evolution.

The availability of efficient hydrogen evolution reaction (HER) catalysts is of high importance for solar fuel technologies aimed at reducing future carbon emissions. Even though Pt electrodes are excellent HER electrocatalysts, commercialization of large-scale hydrogen production technology requires finding an equally efficient, low-cost, earth-abundant alternative. Here, high porosity, metal-organic framework (MOF) films have been used as scaffolds for the deposition of a Ni-S electrocatalyst. Compared with an MOF-free Ni-S, the resulting hybrid materials exhibit significantly enhanced performance for HER from aqueous acid, decreasing the kinetic overpotential by more than 200 mV at a benchmark current density of 10 mA cm(-2). Although the initial aim was to improve electrocatalytic activity by greatly boosting the active area of the Ni-S catalyst, the performance enhancements instead were found to arise primarily from the ability of the proton-conductive MOF to favourably modify the immediate chemical environment of the sulfide-based catalyst.

Bias-Switchable Permselectivity and Redox Catalytic Activity of a Ferrocene-Functionalized, Thin-Film Metal-Organic Framework Compound.

The installation of ferrocene molecules within the wide-channel metal-organic framework (MOF) compound, NU-1000, and subsequent configuration of the modified MOF as thin-film coatings on electrodes renders the MOF electroactive in the vicinity of the ferrocenium/ferrocene (Fc(+)/Fc) redox potential due to redox hopping between anchored Fc(+/0) species. The observation of effective site-to-site redox hopping points to the potential usefulness of the installed species as a redox shuttle in photoelectrochemical or electrocatalytic systems. At low supporting electrolyte concentration, we observe bias-tunable ionic permselectivity; films are blocking toward solution cations when the MOF is in the ferrocenium form but permeable when in the ferrocene form. Additionally, with ferrocene-functionalized films, we observe that the MOF's pyrene-based linkers, which are otherwise reversibly electroactive, are now redox-silent. Linker electroactivity is fully recovered, however, when the electrolyte concentration is increased 10-fold, that is, to a concentration similar to or exceeding that of an anchored shuttle molecule. The findings have clear implications for the design and use of MOF-based sensors, electrocatalysts, and photoelectrochemical devices.

Destruction of chemical warfare agents using metal-organic frameworks.

Chemical warfare agents containing phosphonate ester bonds are among the most toxic chemicals known to mankind. Recent global military events, such as the conflict and disarmament in Syria, have brought into focus the need to find effective strategies for the rapid destruction of these banned chemicals. Solutions are needed for immediate personal protection (for example, the filtration and catalytic destruction of airborne versions of agents), bulk destruction of chemical weapon stockpiles, protection (via coating) of clothing, equipment and buildings, and containment of agent spills. Solid heterogeneous materials such as modified activated carbon or metal oxides exhibit many desirable characteristics for the destruction of chemical warfare agents. However, low sorptive capacities, low effective active site loadings, deactivation of the active site, slow degradation kinetics, and/or a lack of tailorability offer significant room for improvement in these materials. Here, we report a carefully chosen metal-organic framework (MOF) material featuring high porosity and exceptional chemical stability that is extraordinarily effective for the degradation of nerve agents and their simulants. Experimental and computational evidence points to Lewis-acidic Zr(IV) ions as the active sites and to their superb accessibility as a defining element of their efficacy.

MOF functionalization via solvent-assisted ligand incorporation: phosphonates vs carboxylates.

Solvent-assisted ligand incorporation (SALI) is useful for functionalizing the channels of metal-organic framework (MOF) materials such as NU-1000 that offer substitutionally labile zirconium(IV) coordination sites for nonbridging ligands. Each of the 30 or so previous examples relied upon coordination of a carboxylate ligand to achieve incorporation. Here we show that, with appropriate attention to ligand/node stoichiometry, SALI can also be achieved with phosphonate-terminated ligands. Consistent with stronger M(IV) coordination of phosphonates versus carboxylates, this change extends the pH range for retention of incorporated ligands. The difference in coordination strength can be exploited to achieve stepwise incorporation of pairs of ligands-specifically, phosphonates species followed by carboxylate species-without danger of displacement of the first ligand type by the second. Diffuse reflectance infrared Fourier-transform spectroscopy suggests that the phosphonate ligands are connected to the MOF node as RPO2(OH)¯ species in a moiety that leaves a base-accessible -OH moiety on each bound phosphonate.

Ultrahigh surface area zirconium MOFs and insights into the applicability of the BET theory.

An isoreticular series of metal-organic frameworks (MOFs) with the ftw topology based on zirconium oxoclusters and tetracarboxylate linkers with a planar core (NU-1101 through NU-1104) has been synthesized employing a linker expansion approach. In this series, NU-1103 has a pore volume of 2.91 cc g(-1) and a geometrically calculated surface area of 5646 m(2) g(-1), which is the highest value reported to date for a zirconium-based MOF and among the largest that have been reported for any porous material. Successful activation of the MOFs was proven based on the agreement of pore volumes and BET areas obtained from simulated and experimental isotherms. Critical for practical applications, NU-1103 combines for the first time ultrahigh surface area and water stability, where this material retained complete structural integrity after soaking in water. Pressure range selection for the BET calculations on these materials was guided by the four so-called "consistency criteria". The experimental BET area of NU-1103 was 6550 m(2) g(-1). Insights obtained from molecular simulation suggest that, as a consequence of pore-filling contamination, the BET method overestimates the monolayer loading of NU-1103 by ∼16%.

Experimental and computational insights into carbon dioxide fixation by RZnOH species.

Organozinc hydroxides, RZnOH, possessing the proton-reactive alkylzinc group and the CO2 -reactive Zn-OH group, represent an intriguing group of organometallic precursors for the synthesis of novel zinc carbonates. Comprehensive experimental and computational investigations on 1) solution and solid-state behavior of tBuZnOH (1) species in the presence of Lewis bases, namely, THF and 4-methylpyridine; 2) step-by-step sequence of the reaction between 1 and CO2; and 3) the effect of a donor ligand and/or an excess of tBu2Zn as an external proton acceptor on the reaction course are reported. DFT calculations for the insertion of carbon dioxide into the dinuclear alkylzinc hydroxide 12 are fully consistent with (1)H NMR spectroscopy studies and indicate that this process is a multistep reaction, in which the insertion of CO2 seems to be the rate-determining step. Moreover, DFT studies show that the mechanism of the rearrangement between key intermediates, that is, the primary alkylzinc bicarbonate with a proximal position of hydrogen and the secondary alkylzinc bicarbonate with a distal position of hydrogen, most likely proceeds through internal rotation of the dinuclear bicarbonate.